Process of treating petroleum products



the yields of Patented Nov. 25, 1924.

7 UNITED I TE 1,516,720 PATENT OFFICE.

CARLETON ELLIS, OF. MONTGLAIR, NEW JERSEY, ASSIGNOR T ELLIS-FOSTER COM- .PANY, A CORPORATION OF NEW JERSEY.

PROCESS OF TREATING PETROLEUM PRODUCTS. l

To all whom/it may concern:

Be itknown that I, CARLEroN ELLIS, a citizen of the United States," and a resident of Montclair, in the county of Essex and State of New Jersey, have invented certain new and useful Improvements in Processes of Treating Petroleum Products, of which the following is'a specification. p

This invention relates to a method of treating petroleum products and relates especially to a process of cracking petroleum oils under high pressure and at a relatively high temperature or under other suitable conditions such that a mixture of aliphatic and aromatic bodies are produced and ex posing the products of cracking or prefer ably a portion of -the'lighter products to the action of air or oxygen under conditions 'ofselective oxidation whereby various oxidized products are secured which have valuable industrial uses.

An oil heavier than gasoline preferablyis used for the purpose, for example kerosene or oils much heavier than kerosene, includin residiuum and oils ofintermediatespeci c gravity. The oil'is preferably cracked under a relatively high pressure as for exam le 10 to atmospheres and a relatively hig temperature as, for example 800 or 900 C. :The object of these "drastic crack ing conditions is to produce a'product con-- taming a substantial amount (that is to say preferably not less than 5%) ofaromatichydrocarbons as for example benzol, toluol, naphthalene and the like. Preferably I aim to secure at least 5to 10 per cent of aromatic hydrocarbons in the liquid products andthis proportion may be desirably increased to more substantialpropor tions, for example or per cent or even hi her. i

or example kerosene is vaporized and assed through a strongly heated tube uner pressure to form heavler than kerosene. The li ht products will contain some benzol and ot er aromatic hydrocarbons if the cracking has been carr1ed out under sufiiciently drastic conditions. Thus a product containing 10 to 15 per cent of aromatic hydrocarbons may be obtained which may subsequently be oxidized as will be more fully detailed below.

As drastic cracking. produces a considerable quantity of fixed gases which reduce liquid hydrocarbons I may gasoline and products Renewed August 22, 1924.

be separated directly therefrom by means of a diffusion device,v liquefaction opera tions or other procedures. When the cracking has been carried out at a very high temperature a good part of the gas in, some cases'will be hydrogenand by putting this gas through a liquid air apparatus hydrogenmay be obtained in a state of comparative purity.

Theliquid products obtained on condensing the vapors arising from the cracking operation are suitably distilled and various fractions selected as desiredto be subjected to oxidation.

In carrying out the oxidation step I preferably employ a catalyzer such as chromium oxide, vanadium oxide, iron chromate and similar oxidizing catalysts. If desired these may be placed on a support or carrier such as pumica The catalytic material is placed in a tube which is heated in a lead bath to300 to 400 C. 'A temperature of 320 C. is advantageous. Uniform heating and heat control is quite essentialto'the successful operation of the process and conseuently the temperature of the lead bath s ould be carefully watched. Likewise itis desirable to have a thermometer in the exit gases to indicatetheir temperature in order that the rate of flow of the gas through the catalyzing chamber may not be too rapid and thus cool the gases below a desirable oxidizing temperature. The air employed may be washed to remove impurities and i are passed onward to the catalyzing chamher. The amount of oxygen introduced should be carefully proportioned, preferably about per cent being used but the proportion varying with diiierent hydrocarbon mixtures. The amount of-"oxygen (or air) used is preferably less than that required for com lete combustion, and for the best results t e amounts used are substantially less than that required for com lete' combustion, that is the oxygen is 9. out 20%. The exit gases may be treated in various ways preferably they are passed through a cooling chamber in which are cooling coils and inthis chamber any solid crystalline substances, etc., will be deposited to a considerable extent. The vapors from the cool ingchamber then may pass throughan ordinary air-cooled or water-cooled condenser and subsequently ifdesired may be passed over activated carbon or silica gel. Another and preferable method of procedure is to pass the gases into the cooling chamber to collect any fatty acids and other very readily conden'sable substances and to pass the vapors through. a scrubbing tower through which water is passed in order to collect water soluble products of oxidation and finallyto pass througha scrubbing oil or into a scrubbing tower to collect the gasoline and other water insoluble liquids. It

may beadded however that in the water scrubbing apparatus a considerable amount of hydrocarbon may condense and this may be suitably separated. Or the products of oxidation may pass into an air-cooled cons denser, then into a water-cooled condenser and finally may be scrubbed with heavy oil silica gel.

or may be passed over activated carbon or By using an air condenser of large size clogging due to the separation of solid crystalline substances may be very largely avoided the apparatus being cleaned from time to time. The aqueous solution 7 willgenerally be found strongly acid due to the formation of water soluble fatty acids bythe oxidation. These include. not only monocarboxylic acids of the acetic acid type but also dicarboxylic acids.

In this mannerthe various products of oxidation maybe collected and separated in a crude state being subsequently refinedto suchcondit'ion'of purity as may be desired. The oxygen of the air is so completely H utilized in this manner that the process afas noted above and apurified mixture of these gases in the ratio of three volumes of hydrogen to one volume ofnitrogen may be passed under a pressure of".approximately 100 atmospheres or higher into contact with an ammonia catalyst such for example as fused or sintered iron granules composed of very pure iron or other catalyzers suitable for the purpose may be employed. Ammonia is formed and carried away in the exit gases to suitable absorbing agents such for example as sulphuric acid. The by-product acid obtained from refiningof gasoline or other. oils may be used'as anfabsorbing agent. Ammonium sulphate is thus. obtained and constitutes a useful by-product.

What I claim is.;' l i phatic and aromatic .bodies and exposing the products ofcrackingto contactwith a heated catalyzer in thefpresence ofoxygen.

at '1. The method of treating petroleum 2.. The method of treating petroleum which comprises cracking heavy petroleum oils underIhigh pressure and at a relatively high temperature v.to form a mixture of aliphatic hydrocarbons with at least 5 per cent.

of aromatic bodies 'andexposing the 'proda nets of cracking to contact with a heated.

catalyzer in thepresence ofjoxygen.

3. The method of treating petroleum which comprises crackingflheavy petroleum high temperature to form a mixture ofali phatie and aromatic. bodies and exposing the.

products of cracking. to contact with a heatedcatalyzer in the presence of about20 per cent of oxygen supplied as.air..

du'lhe method of treating-"petroleum gasoline for the purpose. ofrmaking. motor spirit while employing a relatively high pressure and a relatively. high temperature to form a mixture of aliphatic and aromatic hydrocarbons, admixinga partlat least oi the lighter products with sink; an amount substantially less than will furnish oxygen sufficient for complete combustion and passing the mixture overa heated catalyzer whereby fatty acids and other productsof oxidation are obtained." I

6. The method of treating-petroleum which comprises cracking oils heavier than gasoline for thepurpose of making motor spirit while employing a relatively high pressure and a relatively high temperature to form a mixture of aliphatic and aromatic hydrocarbons, admixing the lighter products oils under, high pressureand at arelatively v i I 11o treating .i petroleum with air in an amount substantialy less than will furnish oxygen sufiicient for complete combustion and passing the mixture over a heated catalyzer at 320 C. whereby fatty acids and other products of oxidation are obtained.

7. The method of treating petroleum which comprises cracking oils heavier than gasoline for the pur ose of making motor spirit While employing a relatively high pressure and a relatively high temperature to form a mixture of aliphat1c and aromatic hydrocarbons, admixin a part at least of the lighter products w1thhumidified air in an amount substantiall less than will furnish oxygen sufiicient .or complete combustion and passing the mixture over catalyzer heated between 300 and 400 C. whereby fatty acids and other products of oxidation 'h are obtained.

8. The method of treating petroleum which comprises cracking oils heavier than gasoline for the purpose of makin motor spirit while employing a relative y high pressure and a relatively high temperature to form a mixture of aliphatic and aromatic hydrocarbons, admixing apart at least of the lighter products with an oxygen-containing gas in an amount substantia 1y less than will furnish oxygen for complete combustion, passing the mixture over a heated catalyzer whereby fatt acids and other products of oxidation are 0 tained.

9. In the process of oxidizing highly cracked petroleum the step which comprises exposing a mixture of aliphatic and aromatic hydrocarbons, the later present in substantial amount, to the action of an oxidizing catalyst in the resence of air whereby fatty acids and other products of oxidation are obtained.

10. In the process of oxidizing highly cracked petroleum the ste which comprises exposing a mixture of alip atic and aromatic hydrocarbons, the latter present in substantial amount, to the action of an oxidizing catalyst in the presence of humidified air whereby fatty acids and other products of oxidation are obtained.

11. In the process of oxidizing highly cracked petroleum the ste which comprises exposing a mixture of alip atic and aromatic ydrocarbons, the latter present in an amount greater than 5 per cent, to the action of an oxidizing catalyst in the resence of air whereby fatty acids and ot er products of oxidation are obtained.

12. In the process of oxidizing highly cracked petroleum the step which comprises exposing a mixture of volatile aliphatic and aromatic hydrocarbons, the latter present in substantial amount, to the action of an oxidizing catalyst at above 300 C. in the presence of about 20 per cent of oxygen whereby fatty acids and other products of oxidation are obtained.

CARLETON ELLIS. 

